JP2001323208A - Antifouling coating material composition, antifouling coating membrane, vessel or underwater structure coated with the antifouling coating membrane, and antifouling method for vessel outer plate or underwater structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antifouling coating material composition that can form an antifouling coating membrane which can retain hydrolytic properties for a long of time and is excellent in durable antifouling properties. SOLUTION: The objective antifouling coating material composition comprises (a) a polymerizable unsaturated carboxylate metal salt-component unit-including polymer, (b) copper and/or an inorganic copper compound, (c) a metal pyrithione and (d) at least one kind of an organic antifouling agent selected from the group consisting of a triphenylboron amine complex, a tetraphenylboron ammonium salt, tetramethylthiuram disulfide, zincdimethyldithiocarbamate, manganese 2-ethylenebisdithiocarbamate, N,N- dimethyldichorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert.-butylamino-6- cyclopropyl-s-triazine, 4,5-dichloro-2-n-6-octyl-4-isothiazolin-3-one, 2,4,5,6- tetrachloroisophthalonitrile. Further, this invention relates to an antifouling coating membrane formed by coating the composition and curing the resulting membrane, vessels and underwater structures covered with the antifouling coating membrane and an antifouling method for the outside plates of the vessels and underwater structures.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antifouling paint composition,
The present invention relates to an antifouling coating film, a method for coating a ship or underwater structure coated with the antifouling coating film, a ship outer panel or an underwater structure, and more particularly, a hydrolyzability that is long-lasting and a long-term antifouling property. An antifouling paint composition capable of forming an excellent antifouling coating film,
The present invention relates to an antifouling coating film, a ship or underwater structure coated with the antifouling coating film, and a method of antifouling a ship outer panel or underwater structure.

[0002]

BACKGROUND OF THE INVENTION Organic compounds such as organotins have conventionally been used as antifouling agents in marine antifouling paints. The use of antifouling agents is being reviewed. As an alternative antifouling agent, recently, cuprous oxide and copper thiocyanide are used as main components, and various antifouling agents containing no organic tin, that is, non-organic tin-based antifouling agents are blended with the antifouling agent. The improvement of the antifouling performance of an antifouling agent containing, as a main component, etc. has been studied. JP-A-5-171066 discloses (a) polymerizable monomers having two to three double bonds and containing a metal.
0% by weight, 2 to 30% by weight of (b) a vinyl monomer containing a hydroxyl group and / or an amino group, and (c) 40 to 96% by weight of another copolymerizable monomer. Disclosed is an antifouling coating composition containing a polymer as a vehicle component, which is prepared by blending cuprous oxide, zinc white and zinc bis (dimethyldithiocarbamate) as antifouling agents. Is described as being maintained.

[0003] JP-A-8-209005 discloses that R
p-COO-M-OH (wherein, Rp represents a base resin,
M represents a divalent metal atom. The present invention discloses an antifouling resin composition containing, as an active ingredient, a resin having a metal carboxylate in a molecule represented by the formula (1). Have been. It is described that this resin has an excellent antifouling action and can be used for an antifouling paint. JP-A-9-286933 discloses Rp-COOM.
-OH (wherein, Rp represents a base resin and M represents a divalent metal atom); a resin (A) having a metal carboxylate in a molecule represented by an antifouling agent such as cuprous oxide ( An antifouling coating composition comprising B) as an active ingredient is disclosed, wherein M is a divalent metal atom as described above, and rosin (c) is used as a resin component that can be used in combination with the resin (A). Has been raised. The publication states that this composition can exhibit an excellent antifouling effect.

However, in the antifouling paints and coatings comprising the antifouling paint compositions described in the above publications, the resin (copolymer) contained therein is, for example, a copper (meth) acrylate copolymer or the like. The copolymer gradually changes to a copolymer having poor hydrolyzability, and the durability of the antifouling effect is reduced. For this reason, for example, these coating films made of an antifouling coating composition containing conventional cuprous oxide and the like, even if they have an initial antifouling property, the degree of wear decreases over time, and the long-term antifouling property Is not sufficient.

For this reason, launching of ships or underwater structures
It has a stable and appropriate coating film consumption rate from the initial stage of immersion (collectively referred to as the initial stage), and can exhibit excellent antifouling performance against organisms attached to the bottom of a ship for a long time. There has been a demand for the appearance of tin-based antifouling coating compositions. Therefore,
The present inventors have conducted intensive studies and found that a copolymer containing a polymerizable unsaturated carboxylic acid metal compound component unit (a), a copper and / or inorganic copper compound (b), and a metal pyrithione
(c), triphenylboron-amine complex, tetraphenylboron-ammonium salt, 4,5-dichloro-2-
A coating comprising a non-tin-based antifouling coating composition containing a specific organic antifouling agent (d) such as n-6-octyl-4-isothiazolin-3-one is surprisingly moderate in water content. Degradation performance, that is, having an appropriate coating film dissolution rate for a long period of time, and finding out that it is possible to continuously exhibit long-term continuous excellent antifouling performance against organisms attached to ships and the like to complete the present invention. Reached.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above. And a non-tin-based antifouling paint composition capable of forming an antifouling coating film capable of continuously exhibiting excellent antifouling performance against organisms attached to ships or underwater structures for a long period of time. It is intended to be.

The present invention provides an antifouling coating composition formed from this antifouling coating composition, which has a low risk of environmental pollution, has an appropriate coating film consumption rate from the initial stage of immersion, and has excellent long-term antifouling properties. It is an object of the present invention to provide a ship or an underwater structure coated with a membrane and the antifouling coating film, and a method for antifouling the surface of a ship outer panel or an underwater structure using the antifouling paint composition.

[0008]

SUMMARY OF THE INVENTION An antifouling coating composition according to the present invention comprises (a) a copolymer containing a polymerizable unsaturated metal carboxylate component unit, (b) a copper and / or inorganic copper compound, and (c) Metal pyrithiones, (d) triphenylboron-amine complex, tetraphenylboron ammonium salt, tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate,
N, N-dimethyldichlorophenylurea, 2,4,6-
Trichlorophenylmaleimide, 2-methylthio-4-
tert-butylamino-6-cyclopropyl-s-triazine, 4,5-dichloro-2-n-6-octyl-4-
It is characterized by containing at least one kind of organic antifouling agent selected from the group consisting of isothiazizolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile.

In the antifouling coating composition of the present invention, the copolymer (a) containing the polymerizable unsaturated carboxylic acid metal compound unit is (i) the copolymer containing the polymerizable unsaturated carboxylic acid hydroxy metal salt component unit. For example, a copolymer containing a hydroxy metal (meth) acrylate component unit is preferable, and a copolymer containing a hydroxy zinc (meth) acrylate component unit or a hydroxy copper (meth) acrylate component unit is more preferable. It is preferably a copolymer,
(ii) A copolymer containing a hydroxy group-free polymerizable unsaturated carboxylic acid metal salt component unit bound to a metal atom, for example, containing a hydroxy group-free (meth) acrylic acid hydroxy metal salt component unit bound to a metal atom It is preferably a copolymer, and more preferably, a copolymer containing a hydroxy group-free (meth) acrylate zinc salt component unit bonded to a zinc atom or a copper atom or a copolymer containing a (meth) acrylate copper salt component unit. It is preferably a copolymer containing (iii) a polymerizable unsaturated carboxylic acid silyl ester component unit, for example, a copolymer containing a silyl (meth) acrylate component unit.

In the present invention, the above metal pyrithiones
(c) is preferably copper pyrithione or zinc pyrithione. Further, in the present invention, as the organic antifouling agent (d), a triphenylboron-amine complex, tetraphenylboron-ammonium salt or 4,5-dichloro-2-n-octyl-4-isothiazoline-3 is used. -On is preferred.

In the present invention, the metal pyrithione (c) is copper pyrithione or zinc pyrithione, and the organic antifouling agent (d) is a triphenylboron-amine complex or a tetraphenylboron ammonium salt. Are preferred. In the present invention, the metal pyrithiones (c) are copper pyrithione or zinc pyrithione, and the organic antifouling agent (d)
Combinations wherein the component is 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one are preferred.

In the present invention, 1 to 80 parts by weight of the component (a) is added to 100 parts by weight of the total of the components (a) and (b) ((a) + (b)), ) Component is preferably contained in an amount of 20 to 99 parts by weight, and (c) is added to 100 parts by weight of the total of (c) and (d) ((c) + (d)). 5 ingredients
It is preferable to contain the composition in an amount of from 95 to 5 parts by weight and from 95 to 5 parts by weight of the component (d).

[0013] A ship or underwater structure according to the present invention is an antifouling coating film obtained by applying and curing the antifouling coating composition according to any of the above on the surface of a ship outer plate or underwater structure that comes into contact with seawater. It is characterized by being covered with. The antifouling method for a ship outer panel or underwater structure of the present invention comprises applying the antifouling paint composition according to any of the above to the surface of the ship outer panel or underwater structure that comes into contact with seawater, It is characterized in that a film is formed.

According to the antifouling coating composition of the present invention, storage stability for a long period of time is excellent, and a coated and cured coating film formed from the coating composition has an appropriate coating consumption rate immediately after immersion in water, Non-tin-based antifouling paint composition which has a long-lasting property and can form an antifouling coating film that can exhibit excellent antifouling performance against organisms attached to ships or underwater structures for a long period of time Is provided.

The antifouling coating film of the present invention and the ship coated with the coating film are formed from this antifouling coating composition, have a low risk of environmental pollution, and have excellent long-term antifouling properties against attached organisms. ing. In the method for preventing soiling of a ship outer panel according to the present invention, there is little risk of environmental pollution.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The antifouling paint composition according to the present invention, an antifouling coating film, a ship or underwater structure coated with the antifouling coating film, and the antifouling of a ship outer panel or underwater structure are described below. The method will be specifically described. [Antifouling paint composition] First,
Each component contained in the antifouling paint composition will be described sequentially.

<Polymerizable unsaturated carboxylic acid metal compound component>
Unit-containing copolymer (a)> The polymerizable unsaturated carboxylic acid metal compound component unit-containing copolymer (a) includes (i)
A copolymer containing a polymerizable unsaturated carboxylic acid hydroxy metal salt component unit, for example, a copolymer containing a (meth) acrylic acid metal salt component unit, (ii) a polymerizable unsaturated carboxylic acid metal containing no hydroxy group bonded to a metal atom Copolymer containing a salt component unit, for example, a copolymer containing a hydroxy group-free (meth) acrylate metal salt component unit bonded to a metal atom, or (iii) a copolymer containing a polymerizable unsaturated carboxylic acid silyl ester component unit For example, a copolymer containing a silyl (meth) acrylate component unit is used.

The metal atoms constituting the copolymer (a) containing a polymerizable unsaturated carboxylic acid metal compound component unit of the present invention include Ib, IIa, IIb, IIIa and IIa in the periodic table.
Ib, IVa, IVb, Va, Vb, VIb, VII
b, a group VIII metal atom.
u, Zn, Ni, Co, Pb, Al, Mg, Sn, S
Examples thereof include divalent or higher valent metal atoms such as i and Ge. Among them, Cu, Zn and Si are particularly preferable.

The metal atoms constituting the polymerizable unsaturated carboxylic acid metal compound component unit-containing copolymer (a) are Cu, Z
When n, Ni, Co, Pb, Al, and Mg, the following polymerizable unsaturated carboxylic acid metal compound component unit often forms a polymerizable unsaturated carboxylic acid metal salt component unit, and when it is Si, The following polymerizable unsaturated carboxylic acid metal compound component units often form polymerizable unsaturated carboxylic acid metal ester component units.

As the unsaturated carboxylic acid constituting the polymerizable unsaturated carboxylic acid metal compound component unit-containing copolymer (a) of the present invention, specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itacone Acids and the like can be exemplified, but acrylic acid and methacrylic acid are particularly preferred, and these are collectively referred to as (meth) acrylic acid.

Hydroxy metal salt of polymerizable unsaturated carboxylic acid
Component unit-containing copolymer (i) This polymerizable unsaturated carboxylic acid hydroxy metal salt component unit-containing copolymer (i), for example, a (meth) acrylic acid hydroxy metal salt-containing copolymer [hydroxy metal (meth) acrylate component Unit-Containing Copolymer] (i) has a long-term slightly water-soluble property as a vehicle component and has a function of imparting long-term antifouling properties to a coating film. As the union, see JP-A-8-209
005, JP-A-9-286933, the following general formula [I]: R ¹ -COO
During M-OH ····· [I] [Formula [I], R ¹ is _{CH 2 = C (CH 3)} -, CH 2 = C
H-, HOOC-CH = CH-, HOOC-CH = C
(CH ₃ ) — represents an unsaturated bond-containing organic group represented by any one of the formulas, and —COOH may form a metal salt or an ester. M represents the above metal atom, preferably a zinc atom or a copper atom. A copolymer having a component unit derived from a polymerizable unsaturated carboxylic acid hydroxy metal salt monomer in the molecule represented by the formula:

As described above, a copolymer containing a component unit derived from a polymerizable unsaturated carboxylic acid hydroxy metal salt monomer [I] in a molecule represented by the formula [I] is specifically described. A copolymer containing a (meth) acrylic acid hydroxymetal salt component unit, such as a copolymer containing a (meth) acrylic acid hydroxyzinc salt component unit or a (meth) acrylic acid hydroxycopper salt component unit, Obtained by reacting a copolymer having a carboxyl group in the molecule with an oxide or hydroxide of a divalent metal, for example, an oxide or hydroxide of zinc (or copper) in the presence of a small amount of water. be able to.

In this reaction, the above metal oxide or metal hydroxide, for example, zinc (or copper) oxide or hydroxide, is added to 1 mol of carboxyl groups in the above copolymer (resin). And water is used in an amount of 0.1 to 1 mol per 1 mol of carboxyl group. As a specific method for synthesizing the polymerizable unsaturated carboxylic acid metal compound component unit-containing copolymer (i), as described in JP-A-9-286933, a copolymer having a carboxyl group in the molecule is used. Water is added to the polymer in an amount of 0.5 to 5% by weight of the copolymer, and a divalent metal oxide or hydroxide to be added, such as zinc (or copper) oxide or water. The reaction may be carried out at a temperature of 50 to 200 ° C. for 1 to 20 hours by adding an oxide and, if necessary, a very small amount of a polar solvent for preventing turbidity.

The copolymer having a carboxyl group in the molecule is preferably a maleic acid such as (meth) acrylic acid or the like.
To be formed by copolymerizing a polymerizable unsaturated carboxylic acid monomer such as fumaric acid and itaconic acid, and another monomer copolymerizable with these polymerizable unsaturated carboxylic acid monomers. Can be. Various vinyl polymers, polyesters, polyurethanes, natural resins and the like can be used as long as they contain a carboxyl group.

Examples of the other monomer (b) copolymerizable with the polymerizable unsaturated carboxylic acid hydroxy metal salt-containing monomer or the polymerizable unsaturated carboxylic acid monomer (a) include (meth) As the acrylate-based monomers, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate,
Aliphatic monomers such as 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and ethoxyethylene glycol (meth) acrylate;
Alicyclic monomers such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; aromatic monomers such as phenyl (meth) acrylate and benzyl (meth) acrylate; diethyl maleate and diisopropyl maleate , Diisopropyl fumarate, dibutyl itaconate, ethyl zinc stearate maleate, isopropyl copper oleate maleate, hexyl copper versatate maleate, isopropyl zinc laurate zinc fumarate, copper butyl abietic acid fumarate, and the like.

The monomer (b) which can be copolymerized with the polymerizable unsaturated carboxylic acid hydroxy metal salt-containing monomer or the polymerizable unsaturated carboxylic acid monomer (a) includes, specifically, 2, 2-hydroxyethyl (meth) acrylate,
Unsaturated monomers having one hydroxyl group such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxy Examples of the monomer include a dimer or trimer such as propyl (meth) acrylate; and a hydroxyl group-containing unsaturated monomer such as a monomer having a plurality of hydroxyl groups such as glycerol (meth) acrylate.

The above-mentioned monomer containing a polymerizable unsaturated carboxylic acid hydroxy metal salt or another monomer (b) copolymerizable with the polymerizable unsaturated carboxylic acid monomer (a) is specifically exemplified. Are amino- or amide-group-containing monomers such as (meth) acrylamide and butylaminoethyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethyl Aminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth)
Monomers having primary to tertiary amino or amide groups, such as acrylamide, may be mentioned.

Examples of the monomer containing the polymerizable unsaturated carboxylic acid hydroxy metal salt or the other monomer (b) copolymerizable with the polymerizable unsaturated carboxylic acid monomer (a) include: Examples include styrene, vinyl toluene, α-methylstyrene, (meth) acrylonitrile, vinyl acetate, vinyl propionate, and the like. The unsaturated monomers (b) can be used alone or in combination of two or more.

Examples of the oxide or hydroxide of zinc (or copper) which is a divalent metal include zinc oxide, zinc hydroxide [Zn (OH) ₂ ], copper oxide, and copper hydroxide [Cu (OH) ₂ ]
Is raised. As the polar solvent used in the polymerization reaction, alcohol-based solvents such as butanol, ketone-based, ester-based, and ether-based solvents are used.

The copolymer (i) containing the polymerizable unsaturated carboxylic acid hydroxy metal salt component unit, for example, the copolymer containing the (meth) acrylic acid hydroxy metal salt component unit, has a long-term slight water solubility as a vehicle component. It has a function of imparting a long-term antifouling property to a coating film, and the polymerizable unsaturated carboxylic acid hydroxy metal salt component unit-containing copolymer includes a polymerizable unsaturated carboxylic acid hydroxy metal salt unit of a polymerizable monomer. Monomer (a) and the polymerizable unsaturated carboxylic acid hydroxy metal salt-containing monomer and copolymerizable `` other monomer '' (b), which is a polymerizable unsaturated carboxylic acid. The component unit derived from the acid hydroxy metal salt monomer (a) is usually 2 to 65% by weight, and the other monomer copolymerizable with the unsaturated monomer (a) (b)
Those containing the component units derived from them in the remaining amount, that is, 35 to 98% by weight (the total of the component units (a) and (b) are 100% by weight).

In the present invention, the number average molecular weight of the copolymer (i) containing the unsaturated carboxylic acid hydroxy metal salt component unit, for example, the copolymer containing the hydroxy metal (meth) acrylate component unit, is usually 1,000 to 1,000. 50,000, preferably from 3,000 to 20,000, and the glass transition temperature Tg is from -10 ° C to + 60 ° C, preferably from -10 ° C to + 60 ° C.
+ 40 ° C. and the acid value is 80-200.

Containing a hydroxy group bonded to a metal atom
Not containing polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer (i
i) In the antifouling coating composition of the present invention, the polymerizable unsaturated carboxylic acid constituting the polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer (ii) containing no hydroxy group bonded to a metal atom The component unit (a) derived from the metal salt is represented by the general formula [II]: R ¹ —COO-ML _n ... [II] [In the formula [II], R ¹ is CH _{2 C (CH 3) -, CH} 2 = C
H-, HOOC-CH = CH-, HOOC-CH = C
(CH ₃ ) — represents an unsaturated bond-containing organic group, and represents —CO
OH may react with a metal, alcohol, or the like to form a metal salt or ester.

M is the above metal atom, preferably Zn, C
u, Mg, and Si, L represents a hydrocarbon group (R ² ) or an organic acid residue (—OCOR ² ), and M represents Zn, Cu,
In the case of Mg, etc. is preferably L is an organic acid residue, when M is Si, L is preferably a hydrocarbon group (R ^2), R ² in these formulas, Carbon number 1-2
5, preferably in the range of 1 to 20, and represents any of a chain alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an aralkyl group, and n is the valence number of the metal M-1. Indicates a number. ] It is a copolymer containing the component unit derived from the polymerizable unsaturated carboxylic acid metal compound (metallic polymerizable unsaturated carboxylic acid salt) represented by these.

The above L is a carboxylic acid residue (—OCOR ² )
Where the carboxylic acid (H
OCOR ² ) may have a chain, alicyclic, aromatic ring, etc., and is mainly a monovalent carboxylic acid such as propionic acid, valeric acid, oleic acid, linoleic acid, linolenic acid,
Stearic acid, versatic acid, abietic acid (acid contained in rosin), naphthenic acid, (meth) acrylic acid, benzoic acid and the like.

As the polymerizable unsaturated carboxylic acid metal salt monomer represented by the general formula [II], for example, specifically as a (meth) acrylic acid metal salt monomer, specifically, for example, zinc methacrylate: [( _{CH 2 = C (CH 3)} -COO-) 2 Zn],
Zinc acrylate: [(CH ₂ ＣＨCH—COO—) ₂ Z
n], magnesium methacrylate: [(CH ₂ ＣC (C
_{H 3) -COO-) 2 Mg]} , magnesium _{acrylate: [(CH 2 = CH-} COO-) 2 Mg], methacrylic _{copper: [(CH 2 = C (} CH 3) -COO-) 2 Cu] ,
Copper acrylate: [(CH ₂ ＣＨCH—COO—) ₂ C
u], zinc versatate methacrylate: [(CH ₂
ＣC (CH ₃ ) —COO —) ((C ₃ H ₇ ) ₃ C—COO
-) Zn], zinc versatate acrylate: [(C
_{H 2 = CH-COO -)} ((C 3 H 7) 3 C-COO-)
Zn], zinc naphthenate methacrylate: [(CH ₂ =
_{C (CH 3) -COO -)} ( naphthenic acid residue) Zn],
Zinc naphthenate _{acrylate: [(CH 2 = CH-} CO
O -) (naphthenic acid residue) Zn], zinc benzoate _{methacrylate: [(CH 2 = C (} CH 3) -COO -) ((
_{C 6 H 5) COO-) Zn} ], zinc benzoate _{acrylate: [(CH 2 = CH-} COO -) ((C 6 H 5) COO
-) Zn], magnesium benzoate methacrylate:
[(CH ₂ ＣC (CH ₃ ) —COO —) (C ₆ H ₅ COO
-) Mg], versatic acid magnesium _{acrylate: [(CH 2 = CH-} COO -) ((C 3 H 7) 3 C-
COO-) Mg], copper versatate methacrylate:
_{[(CH 2 = C (CH} 3) -COO -) ((C 3 H 7) 3 C
-COO-) Cu], copper benzoate methacrylate:
_{[(CH 2 = C (CH} 3) -COO -) ((C 6 H 5) C
OO-) Cu], copper naphthenate methacrylate: [(C
_{H 2 = C (CH 3)} -COO -) ( naphthenic acid residue) C
u], copper naphthenate acrylate: [(CH ₂ ＣＨCH—
COO-) (naphthenic acid residue) Cu], ethyl-zinc stearate maleate, isopropyl-copper oleate maleate, hexyl-versatate copper maleate, isopropyl-zinc laurate zinc fumarate, butyl abietic acid copper fumarate and the like. Can be.

The above metal salt of a polymerizable unsaturated carboxylic acid [II]
[Other monomers] (b) copolymerizable with [for example, (meth) acrylic acid metal salt monomers (a)] include aliphatic, alicyclic, and aromatic unsaturated monomers. And other monomers that can be copolymerized with the polymerizable unsaturated carboxylic acid constituting the polymerizable unsaturated carboxylic acid hydroxy metal salt-containing copolymer (i). The exemplified unsaturated monomers can likewise be used. Such unsaturated monomers (b) can be used alone or in combination of two or more.

The above-mentioned copolymer (ii) containing a polymerizable unsaturated metal carboxylate component unit which does not contain a hydroxy group bonded to a metal atom, for example, a copolymer containing a metal (meth) acrylate component unit, As a vehicle component, it has a long-term slightly water-soluble property and has a function of imparting a long-term antifouling property to a coating film, and the polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer (i
As i), a polymerizable unsaturated carboxylic acid metal salt monomer (a)
And the copolymerizable `` other monomer '' (b) copolymerizable with the polymerizable unsaturated carboxylic acid metal salt monomer, and is derived from the polymerizable unsaturated carboxylic acid metal salt (a). Is usually 2 to 65% by weight, and the component unit derived from the other monomer (b) copolymerizable with the monomer (a) is the remaining amount, that is, 35 to 98%.
% (The total of component units (a) and (b) is 100% by weight).

Polymerizable unsaturated carboxylic acid metal salt component unit-containing copolymer (ii) obtained by copolymerizing unsaturated monomers (a) and (b), specifically metal (meth) acrylate The number average molecular weight of the component unit-containing copolymer is usually from 5,000 to 1
The glass transition temperature Tg is usually -2.
0 ° C to + 50 ° C. In the antifouling coating composition of the present invention, a method for producing a copolymer containing a polymerizable unsaturated metal carboxylate component unit (ii), specifically, a copolymer containing a metal (meth) acrylate component unit, Is the following (1)-
Any of the methods (3) can be adopted. These copolymers are disclosed in JP-B-7-64985, JP-A-4-80205, JP-A-4-80269, JP-A-4-80270, and JP-A-63-128.
008, JP-A-63-128084, JP-A-1-16809, JP-A-5-171066, and the like or according to the methods disclosed in JP-A-10-15847. , Can be easily manufactured. For example, the following method can be exemplified.

(1) As a first method, a polymerizable unsaturated metal carboxylate monomer, specifically, a metal (meth) acrylate monomer (a) and this monomer (a) And another monomer (b) copolymerizable with an organic solvent, and at a temperature of 60 to 180 ° C. in the presence of a radical polymerization initiator such as tertiary-butyl peroxyoctoate (t-BPO). 5-
It can be formed by solution polymerization for 14 hours.

(2) As a second method, a polymerizable unsaturated carboxylic acid monomer, specifically, (meth) acrylic acid
(A), this monomer (A) and other monomers copolymerizable with (B), and `` saturated aliphatic carboxylic acid metal salt, saturated alicyclic carboxylic acid metal salt, or aromatic carboxylic acid metal salt (C) is mixed with an organic solvent, and solution-polymerized at a temperature of 60 to 180 ° C. for 5 to 14 hours in the presence of a radical polymerization initiator such as tertiary-butyl peroxyoctoate (t-BPO). Can be formed.

(3) As a third method, a polymerizable unsaturated carboxylic acid monomer, specifically, (meth) acrylic acid
(A) and other monomers copolymerizable with this monomer (A) (B)
Is mixed with an organic solvent and subjected to solution polymerization at a temperature of 60 to 180 ° C. for 5 to 14 hours in the presence of a radical polymerization initiator such as tertiary-butyl peroxyoctoate (t-BPO), whereby Forming a copolymer of a saturated carboxylic acid monomer, specifically (meth) acrylic acid (ii) and another monomer (ii) copolymerizable with this monomer (ii), Subsequently, a `` saturated aliphatic carboxylic acid metal salt, saturated alicyclic carboxylic acid metal salt, or aromatic carboxylic acid metal salt '' (c) is reacted with the copolymer, or `` Saturated aliphatic carboxylic acids, saturated alicyclic carboxylic acids or aromatic carboxylic acids '' (c-1) and `` metal salt compounds containing the same kind of metal as described above, and other metal compounds containing the same kind of metal '' (d) ) To form It can be.

Polymerizable unsaturated carboxylic acid silyl ester
Minute unit-containing copolymer (iii) In the antifouling coating composition of the present invention, the polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer (iii), for example, a silyl (meth) acrylate component unit-containing copolymer is General formula [III]: R ¹ —COO—SiL ¹ L ² L ³ ... [III] [In formula [III], R ¹ is CH ₂ ＣC (CH ₃ ) —, CH ₂ ＣC
H-, HOOC-CH = CH-, HOOC-CH = C
It represents an organic group containing an unsaturated bond represented by a formula such as (CH ₃ ) —, and this —COOH may form a metal salt or an ester. L ¹ , L ² , and L ³ may be the same or different from each other, each have from 1 to 20 carbon atoms, and are a chain alkyl group of a hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic group. Shown are hydrocarbon groups and their substitutes. ]
A polymerizable unsaturated carboxylic acid silyl ester monomer (also referred to as a silyl unsaturated carboxylate monomer) represented by
And a copolymer obtained by copolymerizing an unsaturated monomer copolymerizable therewith.

L ¹ , L ² and L ³ bonded to the silicon atom of the polymerizable unsaturated carboxylic acid silyl ester monomer [III] may be the same or different, and each has 1 to 20 carbon atoms. And represents any of a chain (linear or branched) alkyl group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and at least one of L ¹ , L ² and L ³ , preferably Two, particularly preferably three, are preferably a branched alkyl group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and particularly preferably a branched alkyl group or an alicyclic hydrocarbon group. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, s
ec-butyl group, tert-butyl group, isophthyl group,
n-amyl group, isoamyl group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group, cyclohexyl group, cycloalkyl group such as cyclooctyl group,
Examples thereof include aromatic hydrocarbon groups such as a phenyl group, a tolyl group, and a xylyl group.

Specific examples of the polymerizable unsaturated carboxylic acid silyl ester monomer represented by the above general formula [III] include the following silyl (meth) acrylates. For example, trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-
Propylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, trisec-butylsilyl (meth) acrylate, tritert-butylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, Triphenylsilyl (meth) acrylate,
Methyl-diisopropylsilyl (meth) acrylate,
Ethyl-diisopropylsilyl (meth) acrylate,
n-butyl-diisopropylsilyl (meth) acrylate, isobutyl-diisopropylsilyl (meth) acrylate, sec-butyl-diisopropylsilyl (meth) acrylate, phenyl-diisopropylsilyl (meth) acrylate, phenyl-disec-butylsilyl (meth) acrylate , Cyclohexylphenyl-
Diisopropylsilyl (meth) acrylate, phenyl-ditret-butylsilyl (meth) acrylate, phenyl-diisobutylsilyl (meth) acrylate, diethyl-isopropylsilyl (meth) acrylate, diethyl-isopropylsilyl (meth) acrylate, di-n-butyl- Isopropylsilyl (meth) acrylate, diisobutyl-isopropylsilyl (meth) acrylate, disec-butyl-isopropylsilyl (meth) acrylate, dicyclohexylphenyl-isopropylsilyl (meth) acrylate, diphenyl-se
c-butylsilyl (meth) acrylate, diphenyl-
tret-butylsilyl (meth) acrylate, diphenylisobutylsilyl (meth) acrylate, bis (triisopropylsilyl) maleate, bis (triisopropylsilyl) fumarate, ethyl-triisopropylsilylmaleate, isopropyl-triisopropylsilylfumarate, triisopropyl Copper silyl-stearate maleate, triisopropylsilyl-zinc oleate maleate, triisopropylsilyl-zinc abietic maleate, triisopropylsilyl-versatic copper fumarate, triisopropylsilyl-zinc naphthenate fumarate, triisopropylsilyl-abietic acid Specific examples include zinc fumarate.

The "other monomer" (b) copolymerizable with the polymerizable unsaturated carboxylic acid silyl ester (eg, silyl (meth) acrylate (a)) includes aliphatic, alicyclic, Any of aromatic unsaturated monomers and the like may be used. For example, copolymerization with the polymerizable unsaturated carboxylic acid constituting the polymerizable unsaturated carboxylic acid hydroxy metal salt component unit-containing copolymer (i) is possible. As the other possible monomers, the unsaturated monomers exemplified above can be similarly used. Such unsaturated monomers (b) can be used alone or in combination of two or more.

The above-mentioned copolymer (iii) containing a polymerizable unsaturated carboxylic acid silyl ester component unit, for example, a copolymer containing a silyl (meth) acrylate component unit, has a long-term slight water solubility as a vehicle component, and The polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer (iii) has a function of imparting a long-term antifouling property to the polymerizable unsaturated carboxylic acid silyl ester monomer of the polymerizable monomer. body
(A) and the polymerizable unsaturated carboxylic acid silyl ester monomer (A) and copolymerizable `` other monomer '' (B) copolymerizable, polymerizable unsaturated carboxylic acid The component unit derived from the silyl ester monomer (a) is usually 2 to 65% by weight, and the component unit derived from another monomer (b) copolymerizable with the monomer (a) is the remaining amount, that is, 35 to 98%. % (The total of the component units (a) and (b) is 100% by weight).

A polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer (iii) obtained by copolymerizing such unsaturated monomers (a) and (b), for example, silyl (meth)
The number average molecular weight of the acrylate-containing copolymer is usually
5,000 to 100,000, glass transition temperature T
g is usually −20 ° C. to + 50 ° C. As a method for producing the polymerizable unsaturated carboxylic acid silyl ester component unit-containing copolymer (iii) used in the antifouling coating composition of the present invention, a polymerizable unsaturated carboxylic acid silyl ester monomer (specifically, For example, a silyl (meth) acrylate salt monomer (a)) and another monomer (b) copolymerizable with this monomer (a) are mixed with an organic solvent, It can be formed by performing solution polymerization at a temperature of 60 to 180 ° C. for 5 to 14 hours in the presence of a radical polymerization initiator such as oxyoctoate (t-BPO).

In the above-mentioned copolymer (a) such as the above-mentioned copolymers (i), (ii) and (iii), or in the presence of the copolymer (a)
In the antifouling coating film obtained by applying and curing the antifouling coating composition of the present invention containing the above, each of the above copolymerizable monomers (monomers) is cleaved at the copolymerizable double bond site. do it,
It is considered that the resulting component units (monomer units) are linked randomly or in a state arranged in blocks, and copolymers containing monomers having two or more such copolymerizable double bond sites are copolymerized. In such a case, a crosslinked structure may be formed.

<Copper and / or Inorganic Copper Compound (b)> In the antifouling coating composition of the present invention, the average particle diameter and particle size distribution of the copper and / or inorganic copper compound (b) are not particularly limited. For example, especially when the average particle size is 6
Copper and / or inorganic copper compound (b) such as ~ 50 μm
In such a case, there is a tendency that an excellent anti-fouling film is obtained, which is excellent in persistence of hydrolysis, has a constant degree of coating film consumption over a long period of time, and is excellent in long-term anti-fouling properties.

The inorganic copper compound may be any of inorganic copper compounds, such as cuprous oxide, copper thiocyanide (cuprous thiocyanate, copper rhodan), basic copper sulfate and basic acetic acid. Examples thereof include copper, basic copper carbonate, cupric hydroxide, and the like, and preferably, cuprous oxide is used. Such a copper compound is particularly preferably used for coloring paints other than white paints. Such a copper compound, instead of copper,
Alternatively, it may be used alone or in combination of two or more with copper.

<Metal Pyrithiones (c)> In the antifouling coating composition of the present invention, the metal pyrithiones (c) include metals such as sodium, magnesium, calcium, barium, aluminum, copper, zinc, iron and lead. Pyrithiones can be exemplified. Among the above metal pyrithions, copper pyrithione and zinc pyrithione are preferable, and copper pyrithione is more preferable.

<Organic antifouling agent (d)> In the antifouling coating composition of the present invention, as the organic antifouling agent (d), specifically, for example, triphenylboron-amine complex, tetraphenylboron-ammonium salt , Tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, manganese
-2-ethylenebisdithiocarbamate, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-t-butylamino-6-cyclopropyl-s-triadi, 4,5- Dichloro-2-n-octyl-4-isothiazolin-3-one,
2,4,5,6-tetrachloroisophthalonitrile and the like can be mentioned.

Among the above organic antifouling agents, triphenylboron / amine complex, tetraphenylboron / ammonium salt, N, N-dimethyldichlorophenylurea, 2,2
4,6-trichlorophenylmaleimide, 2-methylthio-4-t-butylamino-6-cyclopropyl-s-
Triazine, 4,5-dichloro-2-n-6-octyl-4
-Isothiazolin-3-one, 2,4,5,6-tetrachloroisophthalonitrile are preferred.

Of these, the triphenylboron-amine complex and the tetraphenylboron-ammonium salt are described in detail below. Triphenylboron-amine complex The triphenylboron-amine complex is a complex formed between triferylboron and amines. The amines may be any of primary amines such as aliphatic amines, alicyclic amines, aromatic amines and heterocyclic amines, secondary amines and tertiary amines. Specifically, n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-hexadecylamine , N-octadecylamine, aniline, primary amines such as toluidine; di-n-butylamine, di-n-hexylamine, di-n-octylamine, di-n-decylamine, di-n-dodecylamine, di-n-tridecylamine; Di-n-tetradecylamine, di-n-hexadecylamine, di-n-octadecylamine,
Secondary amines such as diphenylamine; tri-n-propylamine, tri-n-hexylamine, tri-n-octylamine, tri-n-decylamine, tri-n-dodecylamine;
Tertiary amines such as tri-n-tridecylamine, tri-n-tetradecylamine, tri-n-hexadecylamine, tri-n-octadecylamine, triphenylamine; pyridine, 2-picoline, 3-picoline, 4-picoline; 2-
Examples thereof include pyridine such as chloropyridine, 3-chloropyridine, and 4-chloropyridine, and pyridines such as a nuclear-substituted product thereof.

Of these triphenylboron-amine complexes, complexes of triphenylboron with primary amines or pyridines are preferred because of their excellent antifouling performance. Tetraphenylboron ammonium salt In the present invention, the tetraphenylboron ammonium salt is a primary, secondary, tertiary or quaternary ammonium salt of tetraphenylboron. Examples thereof include tetraphenylboron ammonium salts corresponding to monoamines, secondary amines, tertiary amines, and heterocyclic amines.

The tetraphenylboron ammonium salt is described, for example, in Japanese Patent Publication No. 54-1571, and is preferably represented by the following formulas (i) to (vi). (i): (Ph) ₄ B · NH ₄ (Ph: phenyl group), (ii): (Ph) ₄ B · NRH ₃ (Ph: phenyl group, R: aliphatic hydrocarbon group, alicyclic hydrocarbon) And an aliphatic or alicyclic hydrocarbon group having 3 to 25, preferably 4 to 10 carbon atoms, each of which may have a substituent. The group has 6 to 15, preferably 6 to 10 carbon atoms.), (Iii): (Ph) ₄ B · NR ₂ H ₂ (Ph: phenyl group, R: aliphatic hydrocarbon group as described above) Or an aryl group, and a plurality of Rs may be the same or different from each other.), (Iv): (Ph) ₄ B · NR ₃ H (Ph, R: same as above), (v): (Ph) _{4 B · NR 4 (Ph,} R: same as above), (vi) :( Ph) 4 B · (NC 5 H 4) H (Ph: phenyl group, NC ₅ H ₄ H: pyrid Umm).

As the tetraphenylboron ammonium salts (i) to (vi), more specifically, tetraphenylboron ammonium and tetraphenylboron ammonium primary ammonium salt represented by the above formula (ii) Phenylboron / butylammonium [where R = C
₄ H _9], tetraphenyl boron octylammonium
[In the formula (ii), R = C ₈ H ₁₇ ], tetraphenylboron / decylammonium [in the formula (ii), R = C ₁₀ H ₂₁ ], tetraphenylboron / dodecylammonium [in the formula (ii), R =
C ₁₂ H _25], and the like.

Examples of the tetraphenylboron / secondary ammonium salt represented by the above formula (iii) include tetraphenylboron / diphenylammonium [in the formula (iii), two Rs are phenyl groups], tetraphenylboron / dioctyl Ammonium [in the formula (iii), R = C ₈ H ₁₇ ], tetraphenylboron-didecylammonium [in the formula (iii), R = C
₁₀ H ₂₁ ], tetraphenylboron-didodecyl ammonium [in the formula (iii), RＲC ₁₂ H ₂₅ ], and the like.

Examples of the tetraphenylboron / tertiary ammonium salt represented by the above formula (iv) include, for example, tetraphenylboron / triethylammonium [in formula (iv), three R's are an ethyl group], tetraphenylboron / triammonium Hexyl ammonium [in the formula (iv), R = C ₆ H ₁₃ ], tetraphenylboron trioctylammonium [in the formula (iv), R =
C ₈ H ₁₇ ] and tetraphenylboron / tritetradecylammonium [in the formula (iv), R ＝ C ₁₄ H ₂₉ ].

Examples of the tetraphenylboron / quaternary ammonium salt represented by the above formula (v) include, for example, tetraphenylboron / tetraethylammonium [in the formula (v), four R's are ethyl groups], tetraphenylboron / tetraammonium Hexyl ammonium [in the formula (v), R = C ₆ H ₁₃ ], tetraphenylboron / tetraoctylammonium [in the formula (v),
R = C ₈ H ₁₇ ] and tetraphenylboron / tetra-tetradecyl ammonium [in the formula (v), R = C ₁₄ H ₂₉ ]. Examples of the tetraphenylboron / heterocyclic ammonium salt represented by the above formula (vi) include, for example, tetraphenylboron / pyridiniumnium, tetraphenylboron /
Picolinium and the like. Tetraphenylboron / pyridinium nucleus-substituted salts include those obtained by substituting about 1 to 4 alkyls having 1 to 5 carbon atoms into the pyridine nucleus, and about 1 to 4 halogen atoms (F, Cl, Br, etc.). Substituted ones are exemplified.

Among these tetraphenylboron ammonium salts, tetraphenylboron / pyridiniumnium or tetraphenylboron / aliphatic primary ammonium salt is preferred. The tetraphenylboron ammonium salt is used alone or in combination of two or more.

In the antifouling coating composition of the present invention, particularly, among these organic antifouling agents (d), triphenylboron amine complex, tetraphenylboron ammonium salt, 4,5-dichloro-2-n -6-Octyl-octyl-4-isothiazizolin-3-one is preferred. In the antifouling coating composition of the present invention, in particular, copper pyrithione or zinc pyrithione among the above metal pyrithions (c) and triphenylboron-amine complex or tetraphenylboron. It is preferable to use an ammonium salt in combination with copper pyrithione or zinc pyrithione and 4,5-dichloro-
It is preferable to use in combination with 2-n-6-octyl-4-isothiazizolin-3-one because the antifouling performance is excellent.

In the antifouling coating composition of the present invention, a plasticizer such as chlorinated paraffin, a pigment such as zinc oxide (zinc white),
A conventionally known antifouling agent (f) other than the above (ie, the copper and / or inorganic copper compound (b), metal pyrithiones)
(c), excluding organic antifouling agent (d). And inorganic dehydrating agents such as those described below. [Blending Composition of Essential Components] In the antifouling coating composition of the present invention, the copolymer (a) containing the polymerizable unsaturated metal carboxylate compound unit is a copolymer containing the polymerizable unsaturated metal carboxylate compound unit. The sum of the polymer (a) component and the copper and / or inorganic copper compound (b) component ((a) + (b)) 100
1 to 80 parts by weight, preferably 2 to parts by weight,
65 parts by weight, more preferably 15 to 40 parts by weight, the copper and / or inorganic copper compound (b) component is usually 99 to 20 parts by weight, preferably 98 to 35 parts by weight, more preferably 85 parts by weight. It is contained in an amount of up to 60 parts by weight. When the polymerizable unsaturated carboxylic acid metal compound component unit-containing copolymer (a) component and the copper and / or inorganic copper compound (b) component are contained in this range, long-term wear of the coating film surface and The antifouling property tends to be excellent. The copper and / or copper compound (b) is generally 25 to 10000 parts by weight in total, preferably 50 to 5 parts by weight, based on 100 parts by weight of the resin solid content contained in the antifouling coating composition of the present invention.
000 parts by weight.

The copolymer (a) containing the polymerizable unsaturated metal carboxylate compound unit in the antifouling coating composition of the present invention.
And the total of copper and / or inorganic copper compound (b), metal pyrithiones (c) below, and organic antifouling agent (d) below ((a) +
(b) + (c) + (d)) 100 parts by weight of the polymerizable unsaturated carboxylic acid metal compound component unit-containing copolymer (a) component is usually 1 to 78 parts by weight, preferably 2 to 78 parts by weight. It is contained in an amount of 64 parts by weight. When this copolymerizable unsaturated carboxylic acid metal compound component-containing copolymer (a) component is contained in the antifouling paint composition in this range in total, the long-term wear and stain resistance of the coating film surface are improved. Tend to be better.

Further, in the antifouling paint composition of the present invention, the total of component (a) + component (b) + component (c) + component (d) is 100
The component (b) is contained in an amount of 15 to 97 parts by weight, preferably 28 to 96 parts by weight, based on parts by weight. When the copper and / or copper compound (b) is in this range, the antifouling property tends to be excellent. In the antifouling paint composition of the present invention, the metal pyrithione (c) is the total of the components (a), (b), (c) and (d) in the antifouling paint composition (( a) + (b) + (c) + (d)) 100 parts by weight, usually 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight.

In the antifouling coating composition of the present invention, the metal pyrithione (c) is added to 100 parts by weight of the total of the components (c) and (d) ((c) + (d)). Is usually contained in the antifouling coating composition in an amount of 5 to 95 parts by weight, preferably 50 to 90 parts by weight. In the antifouling paint composition of the present invention, the organic antifouling agent (d) is a total of the components (a), (b), (c), and (d) in the antifouling paint composition. ((A) + (b) +
(c) + (d)) 100 parts by weight of the organic antifouling agent (d)
Is usually contained in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight. Organic antifouling agent in such amount
When (d) is contained in the coating composition, there is a tendency that even more excellent antifouling performance against organisms attached to ships or underwater structures can be exhibited over a long period of time.

[ Production of antifouling paint composition ] The antifouling paint composition of the present invention can be produced by appropriately utilizing a conventionally known method. Acid metal compound component unit-containing copolymer (a)
And, in addition to (b) the copper and / or inorganic copper compound, (c) metal pyrithiones, and the organic antifouling agent (d), if necessary, conventionally known various organic antifouling agents and plasticizers , An inorganic dehydrating agent (stabilizer), an anti-sagging / anti-settling agent, a coloring pigment, other film-forming components, a solvent (eg, xylene), etc. in a predetermined ratio at once or in any order and stirring / mixing Then, it can be produced by dissolving and dispersing in a solvent.

<Optional Components> As described above, the antifouling coating composition according to the present invention further comprises, if necessary, other components in addition to the components (a), (b), (c) and (d). Organic antifouling agent components, plasticizers, inorganic dehydrating agents (stabilizers), anti-sagging and anti-settling agents, coloring pigments, and polymerizable unsaturated carboxylic acid copper salt (or zinc salt) Various components other than the polymer (a), such as a coating film forming component and a solvent, may be contained.

<Plasticizer (Chlorinated Paraffin)> Examples of the plasticizer include TCP (tricresyl phosphate), chlorinated paraffin, polyvinyl ethyl ether and the like. These plasticizers can be used alone or in combination of two or more. The plasticizer is incorporated in the antifouling coating composition in an amount of, for example, 0.1 to 10% by weight.

The plasticizer contributes to the improvement of the crack resistance of the coating film obtained from the antifouling coating composition. Among these plasticizers, chlorinated paraffin (chlorinated paraffin) is preferably used. Examples of chlorinated paraffin include Toyo Parax 150 and Toyo Parax A manufactured by Tosoh Corporation.
-70 ". The chlorinated paraffin is contained in an amount of 1 to 50 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the copolymer containing a polymerizable unsaturated metal carboxylate (solid content) (a). It is.

<Inorganic dehydrating agent (stabilizer)> The inorganic dehydrating agent (stabilizer) can further improve the storage stability of the antifouling paint composition.
O ₄ ), synthetic zeolite-based adsorbents (trade name: molecular sieve, etc.), silicates, etc., and anhydrous gypsum,
Molecular sieves are preferably used. Such an inorganic dehydrating agent can be used alone or in combination of two or more. The inorganic dehydrating agent may be contained in the non-tin antifouling coating composition of the present invention in an amount of usually about 0.1 to 10% by weight, preferably about 0.1 to 5% by weight.

<Metal Salt of Carboxylic Acid> The antifouling coating composition of the present invention may further contain a metal salt of carboxylic acid. The metal salt of the carboxylic acid has a molecular weight of usually 50 to 1000, preferably 100 to 6
00 is used. Examples of the carboxylic acid constituting the metal salt of the carboxylic acid include an acid having an alicyclic structure (eg, naphthenic acid) and a carboxylic acid having an aromatic ring structure (eg, α-
(2-carboxyphenoxy) stearic acid), rosin-based resin acids, fatty acids and the like, and naphthenic acid, rosin-based resin acids, and fatty acids are preferred.

The rosin-based resin acid is a resin acid contained in rosin. Examples of the rosin-based resin acid include:
Abietic acid, neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, pimaric acid, dehydroabietic acid, levopimaric acid and the like. The fatty acid may be any of a saturated fatty acid and an unsaturated fatty acid. Examples of the saturated fatty acid include acetic acid, lauric acid,
Examples thereof include those having about 1 to 18 carbon atoms such as myristic acid, stearic acid, and palmitic acid, and examples of unsaturated fatty acids include those having the same number of carbon atoms as acrylic acid and oleic acid.

The metals constituting the metal carboxylate include polyvalent metals such as aluminum, manganese, cobalt, lead, calcium, chromium, copper, iron, magnesium, and the like.
Examples include zinc and nickel, and zinc and copper are preferred. <Anti-sagging / anti-settling agent (thixotropic agent)> Examples of anti-sagging / anti-settling agents include salts of organic viscous Al, Ca, Zn such as stearate salts, lecithin salts, alkyl sulfonates, polyethylene wax, and amide. Wax, hydrogenated castor oil wax type, polyamide wax type and a mixture of both, synthetic fine powder silica, polyethylene oxide type wax and the like, preferably, polyamide wax,
Synthetic fine powder silica, polyethylene oxide-based wax, and organic viscosity-based are used. Examples of such anti-sagging and anti-settling agents include “Dispalon 305” manufactured by Kusumoto Kasei Co., Ltd.
In addition to "Disparon 4200-20", "Disparon A630-
20X "and other products marketed under the trade name.
The anti-sagging / anti-settling agent is incorporated in the antifouling coating composition in an amount of, for example, 0.1 to 10% by weight.

<Pigment> Examples of organic pigments include carbon black, phthalocyanine blue, and navy blue.
Examples of inorganic pigments include neutral and non-reactive pigments such as titanium white, red iron oxide, barite powder, silica, tankar, talc, chalk, iron oxide powder; zinc white (ZnO, zinc oxide), lead Basic and reactive with acidic substances in paint, such as white, lead red, zinc dust, lead oxide powder, etc. (active pigment)
And the like. Note that various colorants such as dyes may be included. Such various pigments are blended in the antifouling coating composition, for example, in a total amount of about 0.5 to 45% by weight.

<Other coating film forming components> Other coating film forming components include, for example, acrylic resin, acrylic silicone resin, unsaturated polyester resin, fluororesin, polybutene resin, silicone rubber, urethane resin (rubber), polyamide Resin, vinyl chloride copolymer resin, chlorinated rubber (resin), chlorinated olefin resin, styrene / butadiene copolymer resin, ethylene-vinyl acetate copolymer resin,
Difficult or water-insoluble resins such as vinyl chloride resins, alkyd resins, coumarone resins, trialkylsilyl acrylate (co) polymers (silyl resins), and petroleum resins (hereinafter also referred to as poorly water-soluble or water-insoluble resins) can give. In the present invention, these resins or rubbers can be used alone or in combination of two or more.

In the present invention, the above-mentioned poorly water-soluble or water-insoluble resin can be used in combination with the following water-soluble resins. Examples of the water-soluble resin include rosin (eg, trade name “Rosin WW”) and monocarboxylic acid. As the monocarboxylic acid, for example, carbon number 9 to
About 19 fatty acids and naphthenic acid are exemplified. Rosin includes gum rosin, wood rosin, tall oil rosin and the like, and any of them can be used in the present invention.
These water-soluble resins can be used alone or in combination of two or more.

<Solvent> In the antifouling paint of the present invention, the above various components are dissolved or dispersed in a solvent. As the solvent used here, for example, various solvents such as an aliphatic type, an aromatic type, a ketone type, an ester type, an ether type, and an alcohol type which are usually blended in an antifouling paint are used. Examples of the aromatic solvent include, for example, xylene and toluene, and the ketone solvent includes
For example, MIBK and the like can be mentioned, and as the ether-based solvent, for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PMAC) and the like can be mentioned.

The antifouling paint composition as described above is used for, for example, ships, fishing materials (eg, ropes, fishing nets, floats, buoys), underwater structures such as water supply / drainage outlets of thermal power plants and nuclear power plants, gulf roads, submarine tunnels. It is excellent in antifouling properties by applying it once to multiple times in accordance with a conventional method on the surface of various base materials such as sludge diffusion prevention films for various marine engineering works such as harbor facilities, canals and waterways, etc. Can be sustainedly released over a long period of time, and can provide a ship or an underwater structure coated with an antifouling coating film having appropriate flexibility and excellent crack resistance even when thickly coated.

That is, the antifouling coating film obtained by applying and curing the antifouling coating composition of the present invention on the surface of various base materials is capable of adhering aquatic organisms such as Aosa, barnacle, Aonori, serpula, oyster, and Fusakomushi. Is excellent in antifouling properties, such as being able to prevent continually for a long time. In particular, the antifouling paint composition of the present invention adheres well to the surface of a substrate such as a ship, even when the substrate is a FRP, steel, wood, aluminum alloy, or the like. Further, the antifouling coating composition of the present invention may be overcoated on an existing antifouling coating film surface.

When the antifouling paint composition of the present invention is applied to the surface of a marine structure, the adhesion of marine organisms can be prevented, the function of the structure can be maintained for a long time, and it can be applied to a fishing net or fishing gear. If applied, fishing nets or fishing gear can be prevented from becoming dirty,
Moreover, there is little risk of environmental pollution. The antifouling coating film of the present invention or the coating film on the surface of a water-contacting part of a ship or an underwater structure coated with the antifouling coating film has a low risk of environmental pollution, and is resistant to organisms attached to the ship or the underwater structure. Excellent long-term antifouling properties.

[0082]

The antifouling paint composition of the present invention is a non-tin antifouling paint composition, comprising the above-mentioned copolymer (a) containing a polymerizable unsaturated metal carboxylate compound unit, copper and / or copper. Since containing an inorganic copper compound (b), metal pyrithiones (c), and an organic antifouling agent (d), a conventional antifouling paint, for example,
Compared to anti-fouling paints containing a copolymer containing copper (meth) acrylate component unit and cuprous oxide, it has a long-term antifouling property in a high-fouling environment such as inland sea, and is moderate from the initial stage of immersion in water A coating film that has a long coating consumption rate, has a long-lasting hydrolytic property, and can exhibit an excellent antifouling performance for aquatic organisms that will adhere to ships or underwater structures for a long time. Can be formed.

The antifouling coating film of the present invention and the antifouling coating film on the surface of a ship or underwater structure are formed from this antifouling coating composition, have a low risk of environmental pollution, and have a long term Excellent antifouling properties. In the method for preventing soiling of a ship outer panel according to the present invention, there is little risk of environmental pollution.

[0084]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, each compound component used in the following Examples and Comparative Examples, its composition, physical properties, manufacturer and distributor are as follows. The copolymers A and B are shown in Table 1, and the copolymers C, D and E are shown in Table 2.
And the copolymers f, G and H are shown in Table 3. (1) Copolymer containing hydroxy zinc (meth) acrylate component unit (A): from 8 parts by weight of methacrylic acid (MAA), 4 parts by weight of methyl methacrylate (MMA), and 28 parts by weight of ethyl acrylate (EA) (A total of 40 parts by weight of these copolymerizable monomers) was dissolved in a solvent (40 parts by weight of butyl acetate and 20 parts by weight of n-butanol) (100 parts by weight in total), and the mixture was dissolved in the presence of polymerization initiator AIBN.
The copolymerization reaction was carried out at 00 ° C. for 6 hours, and the molecular weight (M
W) having a copolymer (a) content of about 8,000 (solid content 40
% By weight).

Table 1 shows the monomer composition at the time of preparing the copolymer (a) and the physical properties of the obtained copolymer (a). This copolymer (a) having a molecular weight of about 8000
0 parts by weight, 4 parts by weight of zinc white and 1 part by weight of water
The reaction was carried out at 20 ° C. for 10 hours to obtain a colorless and transparent liquid containing a hydroxyzinc methacrylate component unit-containing copolymer (A).

To the obtained colorless and transparent liquid, n-butanol was added to adjust the solid content concentration to NV 40%. The copolymer (A) -containing liquid containing the hydroxyzinc (meth) acrylate component unit whose solid content was adjusted in this manner was used in the following Examples and Comparative Examples. (2) (meth) acrylic acid hydroxyzinc salt component unit-containing copolymer (B): 10 parts by weight of methacrylic acid (MAA)
A monomer mixture consisting of 0 parts by weight of methyl methacrylate (MMA) and 30 parts by weight of ethyl acrylate (EA) (total of 40 parts by weight of these copolymerizable monomers) was added to a solvent (40 parts by weight of butyl acetate and 20 parts by weight of n-butanol). ), And subjected to a copolymerization reaction at 100 ° C. for 6 hours in the presence of a polymerization initiator AIBN to give a copolymer (b) -containing material having a molecular weight (MW) of about 8000 ( Solid content 4
0% by weight).

The monomer composition at the time of preparing the copolymer (b),
Table 1 shows the physical properties and the like of the copolymer (b). To 100 parts by weight of the copolymer (b) -containing material (having a molecular weight of about 8000), 5 parts by weight of zinc white and 1 part by weight of water were added and reacted at 120 ° C. for 10 hours. A solution containing the acid hydroxyzinc salt copolymer (B) was obtained. N-Butanol was added to the obtained colorless transparent liquid to obtain a solid content concentration N
V was adjusted to 40%.

The solid content concentration was thus adjusted (meth).
The liquid containing the hydroxy zinc acrylate component unit-containing copolymer (B) was used in the following Examples and Comparative Examples. (3) A copolymer containing a hydroxy group-free zinc (meth) acrylate component unit bound to a zinc atom (C): 8 parts by weight of zinc methacrylate (Zn (MAA) ₂ , manufactured by Asada Chemical Co., Ltd.), methacryl 4 parts by weight of methyl acrylate (MMA) and 28 parts by weight of ethyl acrylate (EA) (total of 40 parts by weight of these copolymerizable monomers) were dissolved in a solvent (40 parts by weight of butyl acetate, n-
Dissolved in 20 parts by weight of butanol (100 parts by weight in total)
Then, a copolymerization reaction was carried out at 100 ° C. for 7 hours in the presence of a polymerization initiator t-BPO to obtain a molecular weight (MW).
Of the copolymer (C) containing about 10,000 (solid content (NV): 40)
% By weight). (4) Copolymer containing a hydroxy group-free (meth) acrylic acid zinc salt component unit bonded to a zinc atom (D): 10 parts by weight of zinc methacrylate (Zn (MAA) ₂ , manufactured by Asada Chemical Co., Ltd.), methacryl 0 parts by weight of methyl acrylate (MMA) and 30 parts by weight of ethyl acrylate (EA) (total of 40 parts by weight of these copolymerizable monomers) were dissolved in a solvent (40 parts by weight of butyl acetate, n-
Dissolved in 20 parts by weight of butanol (100 parts by weight in total)
Then, a copolymerization reaction was carried out at 100 ° C. for 7 hours in the presence of a polymerization initiator t-BPO to obtain a molecular weight (MW).
Of a copolymer (D) containing about 10,000 (solid content (NV): 40)
% By weight). (5) Copolymer containing zinc (meth) acrylate component unit (E): zinc versatate methacrylate [(CH ₂
ＣC (CH ₃ ) —COO —) ((C ₃ H ₇ ) ₃ C—COO
−) Zn] 10 parts by weight, ethyl acrylate (EA) 30
Dissolve parts by weight (total of 40 parts by weight of these copolymerized monomers) in a solvent (40 parts by weight of butyl acetate and 20 parts by weight of n-butanol) (100 parts by weight in total) and cause a copolymerization reaction at 100 ° C. for 7 hours. Gives the molecular weight (M
W) containing a copolymer (E) containing about 10,000 (solid content (N
V): about 40% by weight).

These copolymers (C), (D) and (E)
Table 2 shows data such as physical properties of the product. (6) Copper acrylate component unit-containing copolymer (F): A mixed solution of 30 parts by weight of xylol and 30 parts by weight of n-butanol is kept at 90 ° C., and 27.3 parts by weight of ethyl acrylate (EA) is contained in this solution. Parts by weight of a mixed solution of 6 parts by weight of cyclohexyl methacrylate (CHMA), 6.7 parts by weight of acrylic acid (AAc), and 1 part by weight of a polymerization initiator (AIBN).
The mixture was added dropwise over a period of time, and kept warm for 2 hours after the addition to obtain a solution containing the copolymer (f) having a molecular weight (MW) of about 8000 (solid content: 40%).

To 100 parts by weight of the copolymer (f) having a molecular weight (MW) of about 8000, 24 parts by weight of copper acetate, 33 parts by weight of naphthenic acid and 100 parts by weight of xylol were added, and the mixture was heated at 130 ° C.
Then, acetic acid was removed together with the solvent to obtain a solution containing a copper acrylate copolymer (F) which was a transparent blue liquid.
Xylol was added to the resulting blue transparent solution to adjust the solid content concentration to NV 40% by weight.

Table 3 shows the monomer composition at the time of preparing the copolymer (f), the physical properties of the copolymer (f), and the like. (7) Copper acrylate component unit-containing copolymer (G): 7 parts by weight of copper acrylate [Cu (AAc) ₂ ], copper versatate methacrylate: [(CH ₂ ＣC (CH ₃ ) —COO]
−) ((C ₃ H ₇ ) ₃ C—COO—) Cu] 10 parts by weight,
23 parts by weight of ethyl acrylate (total of 40 parts by weight of these copolymerizable monomers) was dissolved in a solvent (a mixed solvent of 40 parts by weight of butyl acetate and 20 parts by weight of n-butanol) (100 parts by weight in total), and a polymerization initiator was dissolved. 1 in the presence of t-BPO
By carrying out a copolymerization reaction at 00 ° C. for 7 hours, a liquid containing a copolymer (G) having a molecular weight (MW) of about 10,000 (solid content (NV) 40% by weight) was obtained. Table 3 shows the physical properties and the like of the copolymer (G). (8) Copolymer of copper acrylate component unit (H): 70 parts by weight of xylol was charged into a flask equipped with a stirrer, and 90
C., a mixed solution of 60 parts by weight of triisopropylsilyl acrylate, 5 parts by weight of 2-methoxyethyl acrylate, 35 parts by weight of methyl methacrylate and 1 part by weight of polymerization initiator AIBN was added dropwise with stirring over 1 hour.
After completion of the dropwise addition, the temperature was maintained at the same temperature for 6 hours. Then AIBN
A mixture of 1 part by weight and 10 parts by weight of xylene was added dropwise over 20 minutes, and stirring was continued at the same temperature (90 ° C.) for 2 hours to complete the copolymerization reaction, and a silyl acrylate having a molecular weight (MW) of about 7500 was obtained. A liquid containing the system copolymer (H) was obtained.

Xylene was added to the reaction solution to adjust the solid content concentration to NV 50% by weight. The silyl acrylate-containing copolymer (H) solution having the adjusted solid content was used in the following Examples and Comparative Examples. (9) Chlorinated paraffin: Trade name "Toyoparax 15
0 "(average carbon number: 14.5, chlorine content (amount) 50)
%, Viscosity: 12 poise / 25 ° C., specific gravity: 1.25 / 25
(° C, manufactured by Tosoh Corporation) (10) Zinc oxide: Trade name “Zinc Hua No. 3” (Kyushu Hakusui Co., Ltd.)
(11) Soluble anhydrous gypsum: trade name "CaSO4 D-1"
(12) Titanium White: Titanium White R-5N (trade name, manufactured by Sakai Chemical Industry Co., Ltd.) (13) 4,5-Dichloro-2-n-octyl-4-isothiazoline- 3-one: trade name "Sea Nine 211" (manufactured by Rohm and Haas Company, solid content 30% by weight) (14) 2-pyridinethiol-1-oxide copper salt: trade name "copper pyrithione" (manufactured by Ohrin Co., Ltd.) (15) N '-(3,4-dichlorophenyl) -N, N dimethyl urea: trade name "Priventol A6" (manufactured by Bayer K.K.) (16) 2,4,5,6-tetrachloroisophthalo Nitrile: trade name "Marine Side C" (manufactured by San Nopco Co., Ltd.) (17) N- (2,4,6-trichlorophenyl) maleimide: trade name "IT-354" (Ihara Chemical Co., Ltd.)
(18) 2-Methylthio-t-butylamino-6-cyclopropyl-s-triazine: trade name "Ilgarol 10
51 "(manufactured by Nippon Ciba-Gaikey Co., Ltd.) (19) Cuprous oxide: average particle size 3 μm, trade name" NC303 "
(Note: The average particle size of each cuprous oxide was measured using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation), and the average value was used. (20) 2-Pyridinethiol-1-oxide zinc salt: Trade name "Zingo Margin" (manufactured by Orin) (21) Polyethylene oxide wax: Trade name "Dispalon"
4200-20 ”(Kusumoto Kasei Co., Ltd., anti-settling agent, solid content 2)
(0% by weight of xylene paste) (22) Amide fatty acid wax: trade name “Dispalon 63
0-20X ”(manufactured by Kusumoto Kasei Co., Ltd., anti-settling agent, solid content 20)
(23%) Propylene glycol monomethyl ether: trade name “Kuraray PGM” (manufactured by Kuraray Co., Ltd., solvent) (24) Pyridine triphenylboron: trade name “PK boron” (manufactured by Hokuko Chemical Industry Co., Ltd.) <Evaluation criteria for marine organism attachment area (fouling resistance evaluation criteria)> The evaluation criteria are as follows.

5 points: The area where marine organisms adhere is 0%. 4 points: The area where marine organisms adhere is more than 0% and 5% or less. 3 points: The area where marine organisms adhere is more than 5% and 10% or less. 2 points: The area where marine organisms adhere is more than 10% and 25%
Less than. 1 point: The area where marine organisms adhere is more than 25% and 50%
Less than.

0 points: The area where marine organisms adhere is 50%
Exceeds. <Evaluation method of antifouling paint and antifouling coating film> Stationary antifouling test method The antifouling paint was applied to a vinyl chloride plate having a size of 3 mm x 100 mm x 100 mm so that the dry film thickness became 100 to 150 m. After being left to dry at room temperature (about 20 ° C.) for 7 days, it was immersed at a depth of 1.0 m in Nagasaki Bay, and the state of fouling by marine organisms was observed for 12 months.

In the following examples and comparative examples,
Unless otherwise contradicted, "parts" means parts by weight.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

Examples 1 to 17, Comparative Examples 1 to 8 Using the copolymer (resin) -containing liquids A to H obtained in the above Production Examples, antifouling paint compositions having the composition shown in Tables 4 to 6 were used. Was prepared by a conventional method. The antifouling paint composition having the composition shown in Tables 4 to 6 was applied to a vinyl chloride plate according to the above-described test method, dried and immersed in a predetermined test sea area.
Observed for months.

Tables 4 to 6 show the results.

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

[Table 6]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 47/26 A01N 47/26 47/30 47/30 C 55/02 55/02 B 55/08 55 / 08 59/20 59/20 Z B63B 59/04 B63B 59/04 Z C09D 5/16 C09D 5/16 143/04 143/04 F term (reference) 4H011 AD01 BA01 BB06 BB09 BB10 BB13 BB14 BB16 BC18 DA17 DD01 DF03 4J038 CG111 CG141 CJ181 CL001 GA03 GA15 HA066 HA216 JB18 JB27 JB36 JC01 JC06 JC07 JC37 JC38 NA05 PB05 PB07 PC02

Claims (24)

[Claims] 1. A copolymer containing (a) a polymerizable unsaturated carboxylic acid metal compound unit, (b) a copper and / or inorganic copper compound, (c) a metal pyrithione, and (d) triphenylphenylboron amine. Complex, tetraphenylboron ammonium salt, tetramethylthiuram disulfide, zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide,
-Methylthio-4-tert-butylamino-6-cyclopropyl-s-triazine, 4,5-dichloro-2-n-
6-octyl-4-isothiazolin-3-one, 2,
An antifouling coating composition comprising at least one organic antifouling agent selected from the group consisting of 4,5,6-tetrachloroisophthalonitrile. 2. The sum of the components (a) and (b) ((a) + (b))
2. The composition according to claim 1, wherein component (a) is contained in an amount of 1 to 80 parts by weight and component (b) is added in an amount of 20 to 99 parts by weight based on 100 parts by weight.
3. The antifouling coating composition according to item 1. 3. The sum of the components (c) and (d) ((c) + (d))
5 to 95 parts by weight of component (c), 100 parts by weight,
3. The composition of claim 1, wherein the component is present in an amount of 5 to 95 parts by weight.
3. The antifouling coating composition according to item 1. 4. The antifouling paint composition according to claim 1, wherein the copper compound in the component (b) is cuprous oxide. 5. The antifouling coating composition according to claim 1, wherein said metal pyrithione (c) is copper pyrithione or zinc pyrithione. 6. The organic antifouling agent (d) is 4,5-dichloro-2-n-6-octyl-4-isothiazizolin-3-
The antifouling paint composition according to any one of claims 1 to 5, which is turned on. 7. The antifouling coating composition according to claim 1, wherein the organic antifouling agent (d) is a triphenylboron amine complex or a tetraphenylboron ammonium salt. 8. The organic antifouling agent (d), wherein the metal pyrithione (c) is copper pyrithione or zinc pyrithione.
Is 4,5-dichloro-2-n-6-octyl-4-isothiazolin-3-one. 9. The metal pyrithione (c) is copper pyrithione or zinc pyrithione, and the organic antifouling agent (d)
Is a triphenylboron-amine complex or tetraphenylboron-ammonium salt. 10. The polymerizable unsaturated carboxylic acid metal compound component unit-containing copolymer (a) is a copolymer containing a polymerizable unsaturated carboxylic acid hydroxymetal salt component unit. 3. The antifouling coating composition according to item 1. 11. The copolymer (a) containing a polymerizable unsaturated carboxylic acid metal compound component unit has a general formula: R ¹ —COOM—OH (I) _{^1, CH 2 = C (CH 3} ) -, CH 2 =
CH-, HOOC-CH = CH-, HOOC-CH = C
(CH ₃ ) — represents an unsaturated double bond-containing organic group represented by any of the formulas, and —COOH may form a metal salt or an ester. M represents a metal atom. ]
The antifouling paint composition according to any one of claims 1 to 10, wherein the copolymer has a component unit derived from a polymerizable unsaturated carboxylic acid hydroxy metal salt represented by the following formula: 12. The copolymer (a) containing the polymerizable unsaturated metal carboxylate compound unit is a copolymer containing a hydroxy metal (meth) acrylate component unit.
12. The antifouling coating composition according to any one of 11). 13. The copolymer (a) containing a polymerizable unsaturated metal carboxylate component unit as the copolymer containing a hydroxyzinc (meth) acrylate component unit or a hydroxycopper (meth) acrylate component unit. The antifouling coating composition according to any one of claims 1 to 12, which is a containing copolymer. 14. The copolymer (a) containing a polymerizable unsaturated carboxylic acid metal compound component unit is a copolymer containing a hydroxy-free polymerizable unsaturated carboxylic acid metal salt component unit bonded to a metal atom. The antifouling coating composition according to claim 1. 15. The polymerizable unsaturated carboxylic acid metal compound component unit-containing copolymer (a) is represented by the following general formula [II]: R ¹ —COO-ML _n. In [II], R ¹ is CH ₂ ＣC (CH ₃ ) —, CH ₂ ＣC
H-, HOOC-CH = CH-, HOOC-CH = C
(CH ₃ ) — represents an unsaturated bond-containing organic group represented by any one of the formulas, and —COOH may form a metal salt or an ester. M represents a metal atom, L represents a hydrocarbon group (R ² ) or an organic acid residue (—OCOR ² ), wherein R ² has 1 to 25 carbon atoms and is a chain alkyl group; An alicyclic alkyl group, an aromatic hydrocarbon group, or an aralkyl group;
Indicates the number of The antifouling paint composition according to claim 14, which is a copolymer containing a component unit derived from a polymerizable unsaturated metal carboxylate compound represented by the following formula: 16. The copolymer (a) containing the polymerizable unsaturated metal carboxylate component unit is a copolymer containing a hydroxy group-free (meth) acrylic acid metal salt component unit bonded to a metal atom. The antifouling paint composition according to claim 14. 17. The copolymer (a) containing a polymerizable unsaturated metal carboxylate compound unit comprising a zinc or copper salt-free (meth) acrylate containing no hydroxy group bonded to a zinc or copper atom. The antifouling coating composition according to any one of claims 14 to 16, which is a polymer. 18. The copolymer (a) containing a polymerizable unsaturated metal carboxylate component unit comprises a zinc (meth) acrylate or copper salt monomer (a), and the monomer (a) The copolymerizable other monomer (b) is copolymerized, and the component unit derived from the zinc (meth) acrylate or copper salt monomer (a) is used in an amount of 2 to 65% by weight. 35 to 98% by weight of a component unit derived from another polymerizable monomer (b)
The antifouling paint composition according to any one of claims 14 to 17, which is a copolymer containing a polymerizable unsaturated metal carboxylate component unit contained in ((a) + (b) = 100% by weight). 19. The antifouling coating composition according to claim 1, wherein the copolymer (a) containing the polymerizable unsaturated carboxylic acid metal compound component unit is a polymerizable unsaturated carboxylic acid silyl ester component unit copolymer. object. 20. The copolymer (a) containing a polymerizable unsaturated carboxylic acid metal compound component unit has a general formula [III]: R ¹ —COO—Si (L ¹ L ² L ³⁾ ] [III] [In the formula [III], R ¹ is CH ₂ ＣC (CH ₃ ) —, CH ₂ ＣC
H-, HOOC-CH = CH-, HOOC-CH = C
(CH ₃ ) — represents an unsaturated bond-containing organic group represented by any one of the formulas, and —COOH may form a metal salt or an ester. L ¹ , L ² and L ³ may be the same or different from each other, and each have 1 to 2 carbon atoms.
0, a chain alkyl group, an alicyclic alkyl group,
It represents any one of an aromatic hydrocarbon group, an aralkyl group, and a substituted product thereof. 20. The antifouling paint composition according to claim 19, which is a copolymer obtained by copolymerizing a silyl unsaturated carboxylate monomer represented by the formula: and an unsaturated monomer copolymerizable therewith. 21. The copolymer (a) containing a polymerizable unsaturated metal carboxylate component unit is a copolymer obtained by copolymerizing silyl (meth) acrylate and an unsaturated monomer copolymerizable therewith. The antifouling paint composition according to claim 19 or 20. 22. An antifouling coating film formed from the antifouling coating composition according to any one of claims 1 to 20. 23. A surface of a ship outer panel or an underwater structure which comes into contact with seawater is coated with an antifouling coating film obtained by applying and curing the antifouling coating composition according to any one of claims 1 to 21. A ship or an underwater structure. 24. The antifouling coating composition according to claim 1, which is applied to the surface of a ship outer panel or an underwater structure which comes into contact with seawater to form an antifouling coating film. Antifouling method for ship outer panels or underwater structures.